CN104338530A - Loaded gold-platinum-palladium catalyst with anti-sintering property and preparation method thereof - Google Patents
Loaded gold-platinum-palladium catalyst with anti-sintering property and preparation method thereof Download PDFInfo
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Abstract
The invention provides a loaded gold-platinum-palladium catalyst with anti-sintering property. The loaded gold-platinum-palladium catalyst is formed by loading a gold-platinum-palladium alloy nanoparticle on a porous carrier, wherein the weight ratio of platinum and palladium is 1:4-2:1, and the dimension of the loaded gold-platinum-palladium catalyst is less than 10 nanometers. The loaded gold-platinum-palladium catalyst is prepared by utilizing a common one-step photodeposition method and keeps a uniform alloy structure at roasting temperature of higher than 700 DEG C, three metals, namely the gold, the platinum and the palladium, are uniformly distributed in each uniform alloy structure, and the three metals are all at a metal valence and form a single-phase alloy structure. The loaded gold-platinum-palladium catalyst provided by the invention has the characteristics that the prepared gold-platinum-palladium three-metal catalyst has excellent anti-sintering property; the problem that the gold-platinum-palladium catalyst is easy to inactivate by being sintered in high-temperature reaction at temperature of higher than 700 DEG C is solved, and the application of high-temperature catalysis is extended, such as methane activation, automobile tail gas treatment, alkane oxidization and other high-temperature reactions; and a preparation method is simple and suitable for large-scale industrialized production.
Description
Technical field
The invention belongs to nanocatalyst field, specifically provide a kind of load type gold platinum palladium catalyst with high temperature anti-sintering property and preparation method thereof.
Background technology
In recent years, support type Au, Pt, Pd tri-metal nano catalyst has unique catalysis and optics, electricity, magnetic performance and attention with the synergy between its multiple metallic element.Due to the synergy in alloy between gold, platinum, palladium element, support type Au, Pt, Pd tri-metal nano caltalyst reveals than monometallic and the excellent performance of bimetallic.But the as easy as rolling off a log sintering of metal nanoparticle is grown up, also along with phase separation under high temperature (>=700 DEG C) reaction.Sintering phenomenon refers to that nano particle at high temperature occurs that particle migration is assembled herein, becomes larger particles (Phys. Chem. Chem. Phys., 12,2010,13499-13510).And phase separation refers to that atomic migration appears in single-phase Au, Pt, Pd alloying pellet in sintering phenomenon, change the two-phase particle of Fu Jin and rich platinum into, palladium is then dispersed in (Chem. Mater., 22,2010,4282-4294.) in two-phase particle.Above-mentioned sintering phenomenon causes support type three metal alloy nanoparticle structure to keep, and then loses catalytic activity, significantly limit its application.Under raising support type Au, Pt, Pd tri-metal nano catalyst high temperature, the anti-sintering property of (>=700 DEG C) is a difficult problem for research, and having no Au, Pt, Pd catalyst at present can at the report of high temperature (>=700 DEG C) anti-sintering.
Summary of the invention
For the deficiencies in the prior art, technical problem to be solved by this invention is to provide a kind of load type gold platinum palladium catalyst with anti-sintering property, and described anti-agglutinatting property refers under high temperature (>=700 DEG C) roasting, to keep the stable of Au, Pt, Pd nanoparticle size and alloy structure.
Applicant finds under study for action, formed by the content of different metal under accuracy controlling Au, Pt, Pd three metal system and control the size (≤10nm) of Au, Pt, Pd alloy nanoparticle structure, the anti-agglutinatting property of load type gold platinum palladium catalyst under high temperature (>=700 DEG C) can be made to significantly improve, the obtained load type gold platinum palladium catalyst with anti-sintering property.
The present invention adopts following technical scheme:
A kind of load type gold platinum palladium catalyst with anti-sintering property, it is characterized in that, described catalyst is made up of on porous support the load of Au, Pt, Pd alloy nanoparticle, in described Au, Pt, Pd alloy nanoparticle, the weight ratio of platinum and palladium is 1:4 ~ 2:1, and described Au, Pt, Pd alloy nanoparticle is of a size of below 10nm.
Wherein, Au, Pt, Pd alloy nanoparticle in described catalyst keeps homogeneous alloy structure under sintering temperature more than 700 DEG C, described homogeneous alloy structure is of a size of below 10nm, gold in described each homogeneous alloy structure, platinum, palladium three kinds of Metal Distribution evenly, Stability Analysis of Structures, three kinds of described metals are metal state, form single-phase alloy structure.
Porous carrier uniform load of the present invention the Au, Pt, Pd alloy nanoparticle being of a size of below 10nm.In preparation process, through more than 700 DEG C high-temperature roastings, Au, Pt, Pd nucleocapsid structure becomes alloy structure, gold in each Au, Pt, Pd alloy nanoparticle, platinum, palladium three kinds of Metal Distribution evenly, Stability Analysis of Structures, size is all at below 10nm, form single-phase alloy structure, be not separated as the phenomenon of Fu Jin and rich platinum two-phase occurs.
In Au, Pt, Pd alloy nanoparticle of the present invention, the weight ratio of platinum and palladium is 1:4 ~ 2:1, within the scope of this, Au, Pt, Pd nano particle keeps homogeneous alloy structure under sintering temperature more than 700 DEG C, as shown in Figure 6, Au, Pt, Pd three kinds of elemental signals are uniformly distributed completely in single Au, Pt, Pd nano particle, and the Au, Pt, Pd nano particle outside this compositing range, then cannot resist sintering under appearing in more than 700 DEG C sintering temperatures and be separated as the phenomenon of two phase structure, as shown in Figure 8.Formed by the content of different metal under accuracy controlling three metal system, and control the size (≤10nm) of Au, Pt, Pd alloy nanoparticle structure, load type gold platinum palladium catalyst anti-agglutinatting property at high temperature can be made to significantly improve.
Further, the gold containing 0.58 ~ 6.5wt% in described Au, Pt, Pd alloy nanoparticle, the platinum of 0.07 ~ 2.8wt%, the palladium of 0.14 ~ 2.8wt%.
Further, catalyst of the present invention keeps homogeneous alloy structure under 700 DEG C ~ 900 DEG C sintering temperatures.
Play an important role in the particle migration of porous carrier in restriction high-temperature roasting, carrier and Au, Pt, Pd alloy nanoparticle act synergistically, the common anti-agglutinatting property improving Au, Pt, Pd catalyst.
Further, porous carrier of the present invention is mesoporous TiO 2; Further, the specific area of described mesoporous TiO 2 is greater than 400m
2/ g, and there is orderly pore passage structure, hole dimension is greater than 25nm.The orderly pore passage structure of this Large ratio surface sum is conducive to the load of Au, Pt, Pd three metal, is fixed on by nano particle in mesopore orbit, reduces the particle migration between nano particle, and then suppresses growing up of nano particle, realizes the effect of anti-sintering.
The present invention also provides the described preparation method with anti-sintering property load type gold platinum palladium catalyst, and concrete synthesis step is as follows:
1), synthesis has the porous carrier of three-dimensional apertures void structure;
2), be highly dispersed in the duct of porous carrier by a step common light sedimentation by the Au, Pt, Pd trimetal nanoparticles being of a size of below 10nm, obtained catalyst precarsor, in described Au, Pt, Pd trimetal nanoparticles, the weight ratio of platinum and palladium is 1:4 ~ 2:1;
3), by step 2) obtained catalyst precarsor high-temperature roasting more than 700 DEG C, the obtained load type gold platinum palladium catalyst with anti-sintering property.
In said method, described step 2) in a step common light sedimentation refer to that Au, Pt, Pd three kinds of metal precursor are hit a step at ultraviolet lighting reduces jointly, uniform deposition is in porous carrier duct.In catalyst precarsor, Au, Pt, Pd trimetal nanoparticles is nucleocapsid structure, Jin Weihe, and platinum palladium is shell.As shown in Figure 9, various metals presoma uniform adsorption, in porous carrier duct, reduces jointly through UV-irradiation, forms the Au, Pt, Pd trimetal nanoparticles of nucleocapsid structure.Through more than 700 DEG C high-temperature roastings of step 3), Au, Pt, Pd is dispersed in nano particle, and nucleocapsid structure becomes alloy structure, forms Au, Pt, Pd alloying pellet.
Adopt a step common light sedimentation can obtain Au, Pt, Pd nano particle and be highly dispersed at trimetallic catalyst precursor in mesoporous TiO 2 duct, by regulating precursor concentration and controllable three metal composition.As shown in Figure 2, Au, Pt, Pd nano particle (in figure shown in bright spot) is uniformly dispersed in mesoporous TiO 2 duct.
Further, described step 2) described in Au, Pt, Pd trimetal nanoparticles in gold containing 0.58 ~ 6.5wt%, the platinum of 0.07 ~ 2.8wt%, the palladium of 0.14 ~ 2.8wt%.
Further, in described step 3), high-temperature roasting temperature is 700 DEG C ~ 900 DEG C.
Further, described step 2) in Au, Pt, Pd trimetal nanoparticles be carried on method on porous carrier, comprise the steps:
1), by the solution of Au, Pt, Pd three kinds of presomas mix with porous carrier, obtained mixed solution.
2), described mixed solution is obtained after illumination, drying Au, Pt, Pd trimetal nanoparticles and be highly dispersed at catalyst precarsor in the duct of porous carrier.
Further, porous carrier of the present invention is mesoporous TiO 2; Further, the specific area of described mesoporous TiO 2 is greater than 400m
2/ g, and there is orderly pore passage structure, hole dimension is greater than 25nm.
Further, described step 1) intermediary hole titanium dioxide (EP-TiO
2) synthetic method of carrier, its preparation process is as follows:
1) duct size is even, arrangement is orderly, the adjustable mesoporous silicon oxide in aperture, to adopt soft template method to synthesize.
2), using mesoporous silicon oxide as hard template, add the sol solution that hydrochloric acid, acetic acid, titanium source and ethanol are formed, after volatilization, form gel, after overaging and roasting, namely obtain mesoporous TiO 2.
Compared to the prior art, the present invention has following beneficial effect:
1) obtained Au, Pt, Pd trimetallic catalyst has excellent anti-sintering property, keeps homogeneous alloy structure, and is of a size of below 10nm, be uniform-distribution with gold, platinum, palladium three kinds of metals in each homogeneous alloy structure more than 700 DEG C under sintering temperature.
2) solve the problem of easy-sintering inactivation in the pyroreaction of Au, Pt, Pd catalyst more than 700 DEG C, expanded its high temperature catalytic applications, as pyroreactions such as methane activation, vehicle maintenance service, oxidation of alkanes.
3) preparation method is simple, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is mesoporous TiO 2 EP-TiO
2nitrogen adsorption desorption figure;
Fig. 2 is the load type gold platinum palladium catalyst with anti-sintering property of the present invention, gold: platinum: palladium: titania weight ratio=1:1:1:75, the HAADF-STEM after light deposition and particle size statistical chart;
Fig. 3 is the load type gold platinum palladium catalyst with anti-sintering property of the present invention, gold: platinum: palladium: titania weight ratio=1:1:1:75, the EDS spectrogram after light deposition; Wherein, Fig. 3 a is the colored spectrogram of actual measurement of EDS, and Fig. 3 b is the black and white schematic diagram of the colored spectrogram of actual measurement based on EDS.
Fig. 4 is the load type gold platinum palladium catalyst with anti-sintering property of the present invention, gold: platinum: palladium: titania weight ratio=1:1:1:75, the XRD spectra before and after 800 DEG C of roastings;
Fig. 5 is the load type gold platinum palladium catalyst with anti-sintering property of the present invention, gold: platinum: palladium: titania weight ratio=1:1:1:75, the HAADF-STEM after 800 DEG C of roastings and particle size statistical chart;
Fig. 6 is the load type gold platinum palladium catalyst with anti-sintering property of the present invention, gold: platinum: palladium: titania weight ratio=1:1:1:75, the EDS spectrogram after 800 DEG C of roastings; Wherein, Fig. 6 a is the colored spectrogram of actual measurement of EDS, and Fig. 6 b is the black and white schematic diagram of the colored spectrogram of actual measurement based on EDS.
Fig. 7 is load type gold platinum, platinum palladium, the golden palladium catalyst of comparative example, gold: platinum: titania weight ratio=1:1:50, platinum: palladium: titania weight ratio=1:1:50, gold: palladium: titania weight ratio=1:1:50, the XRD spectra after 800 DEG C of roastings;
Fig. 8 is the XRD spectra of Au, Pt, Pd catalyst after 800 DEG C of roastings of different composition, is marked on figure according to the average particle size particle size that Scherrer formulae discovery goes out.Its composition is respectively gold: platinum: palladium: titania weight ratio=0.65:0.07:0.28:100(sample 1); 0.60:0.18:0.22:100(sample 2); 0.58:0.28:0.14:100(sample 3); 0.54:0.38:0.08:100(sample 4); 0.51:0.46:0.03:100(sample 5);
Fig. 9 is the synthesis schematic diagram of load type gold platinum palladium catalyst.
Detailed description of the invention
Below by embodiment, the present invention will be further described.The present invention utilizes the characteristic manner such as Electronic Speculum, elemental scan, X-ray diffraction to analyze Au, Pt, Pd distribution of particles and dimensional conditions, proves that Au, Pt, Pd alloy nanoparticle is evenly distributed on carrier EP-TiO
2mesopore orbit in, and keep homogeneous alloy structure, be of a size of below 10nm, gold, platinum, palladium three kinds of metals are uniform-distribution with in each homogeneous alloy structure, wherein HAADF-STEM refers to angle of elevation annular dark-scanning transmission charge pattern, bright spot in figure is metal nanoparticle, obtains corresponding particle size statistical chart, list in figure by the size statistic of 100 particles.EDS spectrogram refers to the elemental scan of individual particle, and the distribution of element embodies with the signaling point of different colours in scheming.XRD spectra refers to X-ray diffraction, the different phase structures of characterizing metal nano particle, and unimodal expression forms single-phase alloy structure, and bimodal expression forms two phase structure.By XRD spectra, utilize Scherrer formula can calculate single-phase and average particle size particle size (Dc) that is double structure.Scherrer formula is Dc=0.89 λ/(B cos θ) (λ is X-ray wavelength, and B is diffraction maximum halfwidth, and θ is the angle of diffraction).
ICP-AES analyzes and refers to ICP-AES, accurately can measure the tenor in material, be mainly used in the test of two aspect materials compositions: one is composition and the content of catalyst precarsor obtained after characterizing light deposition, and in test light deposition process, whether metal precursor effectively deposits in porous carrier; Two is the composition with the load type gold platinum palladium catalyst of anti-sintering property obtained after sign more than 700 DEG C high-temperature roastings and content, and whether the composition of test calcined catalyst is stablized.After 20mg material hydrofluoric acid and aqua regia dissolution, be mixed with the aqueous solution that Au, Pt, Pd ionic theory total concentration is less than 1ppm, analyze the Precise levels drawing metal through ICP-AES, then be scaled the actual composition of material, represent with weight ratio.Through the test of multiple material, the composition of catalyst precarsor obtained after light deposition forms substantially identical with content and metal precursor, and the composition with the load type gold platinum palladium catalyst of anti-sintering property obtained after more than 700 DEG C high-temperature roastings and content substantially identical with catalyst precarsor.The above results illustrates that metal precursor effectively deposits in porous carrier in light deposition process, and the composition of more than 700 DEG C high-temperature roasting rear catalysts is very stable.
Following embodiment is only not used in for illustration of the present invention and limits the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
embodiment 1: the EP-TiO with meso-hole structure
2
synthesis
1, by 0.5g F127(surfactant), 1.25g KCl(potassium chloride) be added to 50ml 1M HCl(hydrochloric acid) in stir to clarify, add 0.7ml 1,3, add 4.46ml ethyl orthosilicate after 5-trimethylbenzene to react 1 day at 14 DEG C, then by reactant liquor hydro-thermal 1 day at 140 DEG C, after suction filtration drying, micro-wave digestion can obtain mesoporous silicon oxide;
2, by mesoporous silicon oxide prepared by 1.62g step 1,1.02g tetrabutyl titanate, 3ml 12M HCl, 6.9ml HOAc (acetic acid) is added to 90ml EtOH(absolute ethyl alcohol) middle stirring 1-2h, at 40 DEG C, volatilization forms gel, aging 24h at 65 DEG C, 350
oafter C roasting 5h EP-TiO
2.Obtained EP-TiO
2specific area is 445m
2/ g, mesoporous cage is of a size of 26.4nm, and pore volume is 0.70cm
3/ g, the result of its nitrogen adsorption desorption as shown in Figure 1.
embodiment 2: the load type gold platinum palladium catalyst by a step common light deposition preparation with anti-agglutinatting property
Load type gold platinum palladium catalyst preparation process is as follows:
1, the methanol solution (10ml) of Au, Pt, Pd three kinds of presomas (2.26mg gold chloride, 3.44mg chloroplatinic acid and 2.35mg palladium bichloride) is added in quartz ampoule, adds the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, obtain catalyst precarsor after carrying out centrifugal drying, what ICP-AES test detected catalyst precarsor consists of gold: platinum: palladium: titania weight ratio=1:1:1:75.HAADF-STEM characterizes Au, Pt, Pd trimetal nanoparticles in catalyst precarsor and is highly dispersed in the duct of mesoporous TiO 2, obtains average-size at 6.8 ± 1.7nm scope (Fig. 2) by particle size statistics.EDS spectral characterization out each Au, Pt, Pd particle is nucleocapsid structure, and gold element (core) signal in the middle of particle is comparatively strong, and platinum and palladium element are at extra-granular (shell) signal comparatively strong (Fig. 3 a, Fig. 3 b).The main peak that XRD characterizes Au, Pt, Pd particle is be positioned at 38.6 ° and 39.6 ° bimodal, belongs to gold and platinum palladium particle respectively (curve in Fig. 4 a);
3, the catalyst precarsor of preparation in step 2 is placed in Muffle furnace roasting, 800 DEG C of roastings 5 hours are risen to 2 DEG C/min, obtain the load type gold platinum palladium catalyst with anti-sintering property, XRD characterizes in obtained catalyst, the main peak of Au, Pt, Pd nano particle becomes 39.7 ° unimodal compared with before roasting, illustrates that nucleocapsid structure becomes alloy structure (the curve b of Fig. 4).There is no the existence at palladium oxide peak in XRD, illustrate that three kinds of metals are metal state, form single-phase alloy structure.Going out its average particle size particle size by Scherrer formulae discovery is 7.4nm.HAADF-STEM characterizes Au, Pt, Pd alloy nanoparticle and is highly dispersed in the duct of carrier mesoporous TiO 2, average-size is obtained at 8.1 ± 2.3nm scope (as Fig. 5) by particle size statistics, before and after roasting, particle is all within 10nm, illustrates that obtained load type gold platinum palladium catalyst has excellent anti-sintering property.EDS after roasting characterizes each Au, Pt, Pd particle alloy nanoparticle and keeps homogeneous alloy structure, is uniform-distribution with gold, platinum, palladium three kinds of metallic elements (as Fig. 6) in each homogeneous alloy structure.
comparative example 3-5: load type double-metal (golden platinum, platinum palladium and golden palladium) catalyst anti-sintering property compares with load type gold platinum palladium catalyst
Load type double-metal (golden platinum, platinum palladium and golden palladium) catalyst is identical with load type gold platinum palladium catalyst preparation method, all adopts a step common light sedimentation.At fixing metal total content identical and often kind of weight metal is equal, contrast bimetallic and the anti-sintering property of trimetallic catalyst, illustrate the superiority of Au, Pt, Pd trimetallic catalyst anti-sintering property.
embodiment 3: load type gold platinum catalyst
Load type gold platinum catalyst preparation process is as follows:
1, the methanol solution (10ml) of golden platinum two kinds of presomas (3.4mg gold chloride, 5.18mg chloroplatinic acid) is added in quartz ampoule, adds the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, obtain catalyst precarsor after carrying out centrifugal drying, what ICP-AES test detected catalyst precarsor consists of gold: platinum: titania weight ratio=1:1:50.
3, the catalyst precarsor of preparation in step 2 is placed in Muffle furnace roasting, rises to 800 DEG C of roastings 5 hours with 2 DEG C/min, obtain load type gold platinum catalyst.It is bimodal that XRD characterizes its main peak, and respectively near peak position that is golden and platinum, illustrating and occurred being separated, become the mixing of Fu Jin and rich platinum phase, is not that (curve in Fig. 7 a) for homogeneous alloy structure.The average particle size particle size being gone out its rich gold and rich platinum phase by Scherrer formulae discovery is respectively 30.3nm and 25.9nm, illustrates to have occurred that serious migration is assembled through high-temperature roasting its particle, becomes bulky grain.By comparing of embodiment 3 and embodiment 2, visible golden platinum catalyst does not possess anti-sintering property.
embodiment 4: load type platinum palladium catalyst
Load type platinum palladium catalyst preparation process is as follows:
1, the methanol solution (10ml) of platinum palladium two kinds of presomas (5.18mg chloroplatinic acid, 3.54mg palladium bichloride) is added in quartz ampoule, adds the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, obtain catalyst precarsor after carrying out centrifugal drying, what ICP-AES test detected catalyst precarsor consists of platinum: palladium: titania weight ratio=1:1:50.
3, the catalyst precarsor of preparation in step 2 is placed in Muffle furnace roasting, rises to 800 DEG C of roastings 5 hours with 2 DEG C/min, obtain load type gold platinum catalyst.It is bimodal that XRD characterizes its main peak, and respectively near the peak position of platinum and palladium oxide, illustrating and occurred being separated, become the mixing of rich platinum and palladium oxide phase, is not homogeneous alloy structure (the curve b in Fig. 7).The average particle size particle size being gone out its rich platinum and palladium oxide phase by Scherrer formulae discovery is respectively 12.4nm and 17.0nm, illustrates to have occurred that serious migration is assembled through high-temperature roasting its particle, becomes bulky grain.By comparing of embodiment 4 and embodiment 2, can find out, platinum palladium catalyst does not possess anti-sintering property.
embodiment 5: load type gold palladium catalyst
Load type gold palladium catalyst preparation process is as follows:
1, the methanol solution (10ml) of golden palladium two kinds of presomas (3.4mg gold chloride, 3.54mg palladium bichloride) is added in quartz ampoule, adds the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, obtain catalyst precarsor after carrying out centrifugal drying, what ICP-AES test detected catalyst precarsor consists of gold: palladium: titania weight ratio=1:1:50.
3, the catalyst precarsor of preparation in step 2 is placed in Muffle furnace roasting, rises to 800 DEG C of roastings 5 hours with 2 DEG C/min, obtain load type gold platinum catalyst.It is bimodal that XRD characterizes its main peak, and respectively near peak position that is golden and palladium oxide, illustrating and occurred being separated, become the mixing of Fu Jin and palladium oxide phase, is not homogeneous alloy structure (the curve c in Fig. 7).The average particle size particle size being gone out its rich gold and palladium oxide phase by Scherrer formulae discovery is respectively 14.3nm and 13.4nm, illustrates to have occurred serious migration gathering through its particle of high-temperature roasting, becomes bulky grain.By comparing of embodiment 5 and embodiment 2, can find out, golden palladium catalyst does not possess anti-sintering property.
By comparative example 3-5, catalyst does not all possess anti-sintering property to load type double-metal (golden platinum, platinum palladium and golden palladium), and Au, Pt, Pd catalyst of the present invention has excellent anti-sintering property.
embodiment 6: by the anti-sintering property regulating the weight ratio of platinum and palladium to improve load type gold platinum palladium catalyst
Load type gold platinum palladium catalyst preparation process is as follows:
1, respectively by Au, Pt, Pd three kinds of presomas (sample 1:1.11mg gold chloride, 0.18mg chloroplatinic acid and 0.50mg palladium bichloride; Sample 2:1.02mg gold chloride, 0.47mg chloroplatinic acid and 0.39mg palladium bichloride; Sample 3:0.97mg gold chloride, 0.73mg chloroplatinic acid and 0.25mg palladium bichloride; Sample 4:0.92mg gold chloride, 0.97mg chloroplatinic acid and 0.14mg palladium bichloride; Sample 5:0.87mg gold chloride, 1.19mg chloroplatinic acid and 0.05mg palladium bichloride) methanol solution (10ml) be added in quartz ampoule, add the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, after carrying out centrifugal drying, obtain 5 kinds of catalyst precarsors.ICP-AES test detects that its composition is respectively gold: platinum: palladium: the weight ratio=0.65:0.07:0.28:100(sample 1 of titanium dioxide); 0.60:0.18:0.22:100(sample 2); 0.58:0.28:0.14:100(sample 3); 0.54:0.38:0.08:100(sample 4); 0.51:0.46:0.03:100(sample 5).
3,5 kinds of catalyst precarsors of preparation in step 2 are placed in Muffle furnace roasting, rise to 800 DEG C of roastings 5 hours with 2 DEG C/min, obtain the load type gold platinum palladium catalyst of sample 1-5 respectively.The main peak that XRD characterizes sample 1-3 is unimodal, and interpret sample 1-3 is alloy structure (as shown in Figure 8).Go out its average particle size particle size by Scherrer formulae discovery and be respectively 7.3nm, 7.5nm and 8.2nm, all at below 10nm, illustrate that there is excellent anti-sintering property.And its main peak is characterized for sample 4-5, XRD become bimodal, respectively near the peak position of gold and platinum, illustrating and occurred being separated, become the mixing of Fu Jin and rich platinum phase, is not homogeneous alloy structure.The average particle size particle size being gone out its rich gold and rich platinum phase by Scherrer formulae discovery is all greater than 12nm, illustrates to have occurred that serious migration is assembled through high-temperature roasting its particle, becomes bulky grain.The above results shows that sample 4-5 does not all possess anti-sintering property, and sample 1-3 has excellent anti-sintering property.The existence at equal non-oxidation palladium peak in the XRD of five kinds of samples, illustrates that three kinds of metals are metal state.By above result, the weight ratio of platinum and palladium is that the Au, Pt, Pd trimetallic catalyst of 1:4 ~ 2:1 keeps homogeneous alloy structure under sintering temperature more than 700 DEG C, and alloy structure is of a size of below 10nm.
embodiment 7-8: by the anti-sintering property regulating sintering temperature to improve load type gold platinum palladium catalyst
embodiment 7: the load type gold platinum palladium catalyst by 700 DEG C of roasting preparations with anti-agglutinatting property
Load type gold platinum palladium catalyst preparation process is as follows:
1, the methanol solution (10ml) of Au, Pt, Pd three kinds of presomas (2.26mg gold chloride, 3.44mg chloroplatinic acid and 2.35mg palladium bichloride) is added in quartz ampoule, adds the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, obtain catalyst precarsor after carrying out centrifugal drying, what ICP-AES test detected catalyst precarsor consists of gold: platinum: palladium: titania weight ratio=1:1:1:75.
3, the catalyst precarsor of preparation in step 2 is placed in Muffle furnace roasting, rises to 700 DEG C of roastings 5 hours with 2 DEG C/min, obtain the load type gold platinum palladium catalyst with anti-sintering property.Going out its average particle size particle size by XRD and Scherrer formulae discovery is 7.8nm, illustrates that obtained load type gold platinum palladium catalyst has excellent anti-sintering property.
embodiment 8: the load type gold platinum palladium catalyst by 900 DEG C of roasting preparations with anti-agglutinatting property
Load type gold platinum palladium catalyst preparation process is as follows:
1, the methanol solution (10ml) of Au, Pt, Pd three kinds of presomas (2.26mg gold chloride, 3.44mg chloroplatinic acid and 2.35mg palladium bichloride) is added in quartz ampoule, adds the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, obtain catalyst precarsor after carrying out centrifugal drying, what ICP-AES test detected catalyst precarsor consists of gold: platinum: palladium: titania weight ratio=1:1:1:75.
3, the catalyst precarsor of preparation in step 2 is placed in Muffle furnace roasting, rises to 900 DEG C of roastings 5 hours with 2 DEG C/min, obtain the load type gold platinum palladium catalyst with anti-sintering property.Going out its average particle size particle size by XRD and Scherrer formulae discovery is 9.2nm, illustrates that obtained load type gold platinum palladium catalyst has excellent anti-sintering property.
embodiment 9-10: by the anti-sintering property regulating Au, Pt, Pd content to improve load type gold platinum palladium catalyst
embodiment 9:
Load type gold platinum palladium catalyst preparation process is as follows:
1, by Au, Pt, Pd three kinds of presomas (sample 1:4.44mg gold chloride, 0.72mg chloroplatinic acid and 2.0mg palladium bichloride; Sample 2:4.08mg gold chloride, 1.88mg chloroplatinic acid and 1.56mg palladium bichloride; Sample 3:3.88mg gold chloride, 2.92mg chloroplatinic acid and 1.0mg palladium bichloride) methanol solution (10ml) be added in quartz ampoule, add the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, after carrying out centrifugal drying, obtain 3 kinds of catalyst precarsors.ICP-AES test detects that its composition is respectively gold: platinum: palladium: the weight ratio 0.65:0.07:0.28:25(sample 1 of titanium dioxide); 0.60:0.18:0.22:25(sample 2); 0.58:0.28:0.14:25(sample 3).
3,3 kinds of catalyst precarsors of preparation in step 2 are placed in Muffle furnace roasting, rise to 800 DEG C of roastings 5 hours with 2 DEG C/min, obtain the load type gold platinum palladium catalyst with anti-sintering property of sample 1-3 respectively.Go out its average particle size particle size by XRD and Scherrer formulae discovery and be below 10nm, illustrate that obtained load type gold platinum palladium catalyst has excellent anti-sintering property.
embodiment 10:
Load type gold platinum palladium catalyst preparation process is as follows:
1, by Au, Pt, Pd three kinds of presomas (sample 1:11.1mg gold chloride, 1.8mg chloroplatinic acid and 5.0mg palladium bichloride; Sample 2:10.2mg gold chloride, 4.7mg chloroplatinic acid and 3.9mg palladium bichloride; Sample 3:9.7mg gold chloride, 7.3mg chloroplatinic acid and 2.5mg palladium bichloride) methanol solution (10ml) be added in quartz ampoule, add the carrier EP-TiO prepared in 100mg embodiment 1
2, after logical argon gas 0.5h removes oxygen, stirring and adsorbing 1h, obtains mixed solution;
2, the mixed solution that step 1 obtains is placed in 25 DEG C of water-baths, under 300W xenon lamp, irradiates 2h, after carrying out centrifugal drying, obtain 3 kinds of catalyst precarsors.ICP-AES test detects that its composition is respectively gold: platinum: palladium: the weight ratio 0.65:0.07:0.28:10(sample 1 of titanium dioxide); 0.60:0.18:0.22:10(sample 2); 0.58:0.28:0.14:10(sample 3).
3,3 kinds of catalyst precarsors of preparation in step 2 are placed in Muffle furnace roasting, rise to 800 DEG C of roastings 5 hours with 2 DEG C/min, obtain the load type gold platinum palladium catalyst with anti-sintering property of sample 1-3 respectively.Go out its average particle size particle size by XRD and Scherrer formulae discovery and be below 10nm, illustrate that obtained load type gold platinum palladium catalyst has excellent anti-sintering property.
Claims (10)
1. one kind has the load type gold platinum palladium catalyst of anti-sintering property, it is characterized in that, described catalyst is made up of on porous support the load of Au, Pt, Pd alloy nanoparticle, in described Au, Pt, Pd alloy nanoparticle, the weight ratio of platinum and palladium is 1:4 ~ 2:1, and described Au, Pt, Pd alloy nanoparticle is of a size of below 10nm.
2. catalyst according to claim 1, it is characterized in that, Au, Pt, Pd alloy nanoparticle in described catalyst keeps homogeneous alloy structure under sintering temperature more than 700 DEG C, described homogeneous alloy structure is of a size of below 10nm, gold in described each homogeneous alloy structure, platinum, palladium three kinds of Metal Distribution are even, three kinds of described metals are metal state, form single-phase alloy structure.
3. catalyst according to claim 2, is characterized in that, described catalyst keeps homogeneous alloy structure under 700 DEG C ~ 900 DEG C sintering temperatures.
4. catalyst according to claim 1, is characterized in that, the gold containing 0.58 ~ 6.5wt% in described Au, Pt, Pd alloy nanoparticle, the platinum of 0.07 ~ 2.8wt%, the palladium of 0.14 ~ 2.8wt%.
5. the catalyst according to any one of claim 1-4, is characterized in that, described porous carrier is mesoporous TiO 2.
6. catalyst according to claim 5, is characterized in that, the specific area of described mesoporous TiO 2 is greater than 400m
2/ g, and there is orderly pore passage structure, hole dimension is greater than 25nm.
7. the preparation method with anti-sintering property load type gold platinum palladium catalyst according to claim 1, is characterized in that comprising the steps:
1), synthesis has the porous carrier of three-dimensional apertures void structure;
2), be highly dispersed in the duct of porous carrier by a step common light sedimentation by the Au, Pt, Pd trimetal nanoparticles being of a size of below 10nm, obtained catalyst precarsor, in described Au, Pt, Pd trimetal nanoparticles, the weight ratio of platinum and palladium is 1:4 ~ 2:1;
3), by step 2) obtained catalyst precarsor high-temperature roasting more than 700 DEG C, the obtained load type gold platinum palladium catalyst with anti-sintering property.
8. preparation method according to claim 7, is characterized in that, the gold containing 0.58 ~ 6.5wt% in described Au, Pt, Pd trimetal nanoparticles, the platinum of 0.07 ~ 2.8wt%, the palladium of 0.14 ~ 2.8wt%.
9. preparation method according to claim 7, is characterized in that, described high-temperature roasting temperature is 700 DEG C ~ 900 DEG C.
10. the preparation method according to any one of claim 7-9, is characterized in that, described step 2) comprise the steps:
1), by the solution of Au, Pt, Pd three kinds of presomas mix with porous carrier, obtained mixed solution;
2), described mixed solution is obtained after illumination, drying Au, Pt, Pd trimetal nanoparticles and be highly dispersed at catalyst precarsor in the duct of porous carrier.
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| WO2016193295A1 (en) * | 2015-06-03 | 2016-12-08 | IFP Energies Nouvelles | Catalyst comprising a porous support, the pores of which contain metal particles having a "sea urchin" morphology |
| CN106732548A (en) * | 2016-11-24 | 2017-05-31 | 中国石油大学(华东) | A kind of surface modification method of loaded platinum catalyst |
| CN112007691A (en) * | 2020-09-18 | 2020-12-01 | 中海油天津化工研究设计院有限公司 | Platinum-palladium bimetallic catalyst and preparation method and application thereof |
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| CN101829565A (en) * | 2010-04-15 | 2010-09-15 | 上海电力学院 | Preparation method of PtRu/C binary alloy nano catalyst |
| CN103402638A (en) * | 2011-03-04 | 2013-11-20 | 庄信万丰股份有限公司 | Alloy-comprising catalyst, method of preparation and uses |
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| WO2006045606A1 (en) * | 2004-10-29 | 2006-05-04 | Umicore Ag & Co Kg | Method for manufacture of noble metal alloy catalysts and catalysts prepared therewith |
| CN101829565A (en) * | 2010-04-15 | 2010-09-15 | 上海电力学院 | Preparation method of PtRu/C binary alloy nano catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016193295A1 (en) * | 2015-06-03 | 2016-12-08 | IFP Energies Nouvelles | Catalyst comprising a porous support, the pores of which contain metal particles having a "sea urchin" morphology |
| FR3036979A1 (en) * | 2015-06-03 | 2016-12-09 | Ifp Energies Now | CATALYST COMPRISING A POROUS CARRIER IN WHICH ARE METALLIC PARTICLES HAVING "OURSIN" TYPE MORPHOLOGY. |
| CN106732548A (en) * | 2016-11-24 | 2017-05-31 | 中国石油大学(华东) | A kind of surface modification method of loaded platinum catalyst |
| CN106732548B (en) * | 2016-11-24 | 2019-02-15 | 中国石油大学(华东) | A kind of surface modification method of loaded platinum catalyst |
| CN112007691A (en) * | 2020-09-18 | 2020-12-01 | 中海油天津化工研究设计院有限公司 | Platinum-palladium bimetallic catalyst and preparation method and application thereof |
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